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1.
The complexation of the uranyl ion with humic acid is investigated. The humic acid ligand concentration is described as the concentration of reactive humic acid molecules based on the number of humic acid molecules, taking protonation of functional groups into account. Excess amounts of U(VI) are used and the concentration of the humic acid complex is determined by the solubility enhancement over the solid phase. pH is varied between 7.5 to 7.9 in 0.1M NaClO4 under normal atmosphere and room temperature. The solubility of U(VI) in absence of humic acid is determined over amorphous solid phase between pH 4.45 and 8.62. With humic acid, only a limited range of data can be used for the determination of the complexation constant because of flocculation or sorption of the humic acid upon progressive complexation. Analysis of the complex formation dependency with pH shows that the dominant uranyl species in the concerned pH range are UO2(OH)+ and (UO2)3(OH)5 +. The complexation constant is evaluated for the humate interaction with the to UO2(OH)+ ion. The stability constant is found to be logβ = 6.94±0.3 l/mol. The humate complexation constant of the uranyl mono-hydroxo species thus is significantly higher than that of the nonhydrolyzed uranyl ion (6.2 l/mol). Published data on the Cm3+, CmOH2+ and Cm(OH)2 + humate complexation are reevaluated by the present approach. The higher stability of the hydrolysis complex is also found for Cm(III) humate complexation.  相似文献   

2.
The sorption of UO2 2+ from aqueous solution on attapulgite was investigated as a function of contact time, solid content, pH, ionic strength, foreign ions, humic acid (HA), and fulvic acid (FA) under ambient conditions by using batch technique. The attapulgite sample was characterized by XRD and FTIR in detail. The results indicated that the sorption of UO2 2+ was strongly dependent on pH and ionic strength. The sorption of UO2 2+ on attapulgite increased quickly with rising pH at pH < 6.5, and decreased with increasing pH at pH > 6.5. The presence of HA or FA enhanced the sorption of UO2 2+ on attapulgite obviously at low pH because of the strong complexation of surface adsorbed HA/FA with UO2 2+ on attapulgite surface. Sorption of UO2 2+ on attapulgite was mainly dominated by ion-exchange or outer-sphere surface complexation at low pH values, but by inner-sphere surface complexation at high pH values. The results indicate that attapulgite is a very suitable adsorbent for the preconcentration and solidification of UO2 2+ from large volumes of aqueous solutions because of its negative surface charge and large surface areas.  相似文献   

3.
The interaction of UO2 2+ with various humic acids (HA's) has been studied by capillary zone electrophoresis (CZE). The experiments were done in 10 mM acetate buffer with pH 3.3 and 4.0, to avoid hydrolysis of uranium. It was found that in slightly acidic media and low HA concentration (<3 mM), two complexes with uranium(VI) are formed by fast kinetics and uranyl migrates as cationic species. Electrophoretic mobilities are decreasing with the increasing HA/uranium ratio and a low soluble neutral compound is also formed. In addition, it was found that at HA concentrations higher than 3 mM negatively charged species are formed. Similar results were obtained for HA's of different origin (soil, peat, coal derived, IHSS standards). Conditional stability constants of the complexes UO2 2+-HA for Fluka I HA, were estimated to be log 1 = 4.18±0.06 and log 2 = 7.28±0.18.  相似文献   

4.
Complexes of UO2 2+, Ce3+ and Nd3+ (M) with acetohydroxamic acid (AHA or L) in an aqueous solution have been investigated by the pH-spectral titration method at 25 °C in an aqueous medium of 1.0 M NaClO4 ionic strength. Cerium(III) and neodymium(III) form [ML]2+, [ML2]+, [ML3] complexes with acetohydroxamic acid, while in case of UO2 2+ form [UO2L]+, [UO2L2] complexes with acetohydroxamic acid. Data processing with SQUAD program calculates the best values for the stability constants from pH-spectrophotometric titration data. The protonation constant obtained was pK1 = 9.15 ± 0.04 at 25 °C. The stability constants for acetohydroxamic acid with UO2 2+, Ce3+ and Nd3+ were β1 = 7.22 ± 0.011, β2 = 14.89 ± 0.018 for UO2 2+ and β1 = 5.05 ± 0.062, β2 = 10.60 ± 0.076, β3 = 16.23 ± 0.088 for Ce3+ and β1 = 5.90 ± 0.028, β2 = 12.22 ± 0.038, β3 = 18.58 ± 0.042 for Nd3+, respectively.  相似文献   

5.
A general model, the so called Mean Molecular Weight Model (MMWM), of complexation of metal cations (Mez+) with macromolecular polyanions of humic acid (HAp-) is proposed. The model is based on the results of previous studies of the electrophoretic mobility of humate complexes and assumes that the complexation proceeds by consecutive neutralization of the dissociated carboxyl groups of the central polyanion HAp- with Mez+ cations. It reflects the macromolecular character of humic acid, applies molar concentrations of reacting components with equations for stability constants and incorporates also the mean charge of humic macromolecules. The model has been verified with experimental data obtained in the study of complexation of Eu(III) with Aldrich humic acid using ion exchange (Amberlite IR-120), over a broad range of [Eu] to [HA] ratio, at pH 4 and 7.  相似文献   

6.
The complexation reactions of dibenzo-18-crown-6 (DB18C6) with Ce3+, Y3+, UO22 +\mathrm{UO}_{2}^{2 +} and Sr2+ cations were studied in acetonitrile–dioxane (AN–dioxane) binary solvent solutions at different temperatures by the conductometric method. The stability constants of the resulting 1:1 complexes were determined from computer fitting of the conductance–mole ratio data. The results show that dibenzo-18-crown-6 does not exhibit selectivity for the cation whose ionic size is closest to the cavity size of this macrocyclic ligand in AN–dioxane binary solvent solutions. A nonlinear relationship was observed between the stability constants (log 10 K f) of these complexes with the composition of the AN–dioxane binary solvent. Values of thermodynamic parameters (DHc°, DSc°\Delta H_{\mathrm{c}}^{\circ}, \Delta S_{\mathrm{c}}^{\circ}) for complexation reactions were obtained from the temperature dependence of the stability constants. The results show that the values along with the sign of these parameters are influenced by the nature and composition of the mixed solvent.  相似文献   

7.
The interactions of Ca2+ and Mg2+ with [UO2(CO3)3]4? were studied by calcium ion selective electrode potentiometry and spectrophotometry. The stability constants of ternary Ca‐UO2‐CO3 and Mg‐UO2‐CO3 complexes were determined with calcium ion selective electrode potentiometry and optical absorption spectrophotometry, respectively. The enthalpies of complexation for two successive complexes, [CaUO2(CO3)3]2? and [Ca2UO2(CO3)3](aq), were determined for the first time by microcalorimetry. The data help to revise the speciation of uranium(VI) species under seawater conditions. In contrast to the previously accepted assumption that the highly negatively charged [UO2(CO3)3]4? is the dominant species, the revised speciation indicates that the dominant aqueous uranium(VI) species under seawater conditions is the neutral [Ca2UO2(CO3)3](aq). The results have a significant impact on the strategies for developing efficient sorption processes to extract uranium from seawater.  相似文献   

8.
Chloridrate of pyridoxine (vitamin B6) reacts with UO2(NO3)2·6H2O in acetonitril containing triethylamine to give the complex salt [UO2(PN)2(H2O)]Cl2. The structure of the novel compound was analyzed by single crystal X‐ray diffraction affording the centrosymmetric triclinic space group . In [UO2(PN)2(H2O)]2+ two zwitterionic pyridoxine molecules complex the uranium atom in a planar manner with a water molecule achieving the coordination of a semi planar pentagon. The two uranyl oxo ligands set the axis of a distorted pentagonal bipyramide. The ability of vitamin B6 pyridoxine to react with UO22+ allowing the chelation of one uranium atom represents a very specific model of assimilation of uranium by living beings. It could also explain the serious damages caused by heavy or radioactive metals like uranium since their complexation “in vivo” by enzymatic systems like pyridoxal phosphate‐containing enzymes would lead to a modification of the prosthetic groups of the metalloenzymes with loss of their catalytic activities.  相似文献   

9.
The kinetics of complexation (C) and decomplexation (D) reactions between Eu(III) and Aldrich humic acid (HA) was investigated as a function of pH (pH 4, 5, 6, 7 and 8) in the system Eu(III) - HA - Amberlite IR-120(Na) (I = 0.1). The derivation of the kinetic differential equations was based on the reactions of Eu3+ with, so called, strong (HAS) and weak (HAW) carboxylic groups of HA formulated in accordance with the new complexation model.1 The differential equations determining d[EuaHAS]/dt and d[EubHAW]/dt have the classical form applicable for reversible reactions where the forward reaction is the C-reaction and the reverse one is the D-reaction. Kinetic model used for the evaluation of experimental data includes these differential equations and the film diffusion model of sorption of Eu3+ on Amberlite IR-120(Na).  相似文献   

10.
The complexation of humic acid from Azraq Oasis with two heavy metal ions Cd(II) and Zn(II) was investigated at pH 4 and 5 under constant ionic strength of 0.1 and at different temperatures (25, 35, 45, 55 and 65 °C). This investigation was done by using Schubert's ion-exchange equilibrium method, and its modified version.The derived conditional stability constants (log βn) for these two metal-humate complexes were determined; they formed 1:1 and 1:2 complexes. It was found that the conditional stability constants (log βn) increased by increasing pH and temperatures for all metal-humate complexes. It was found that the conditional stability constant log β1 for Cd-humate is bigger than Zn-humate at all the desired temperatures and at pH 4 and 5.The derived constants and their temperature dependences have been used to calculate the corresponding thermodynamic parameters ΔG, ΔH, and ΔS, the results indicate that the stability of these complexes derives from very favorable entropy.  相似文献   

11.
The surface property of attapulgite was investigated by N2-BET surface area and zeta potential analysis in this paper. Solution pH had a remarkable effect on the sorption process, indicated an inner-sphere complexation. Humic acid (HA) in the solution enhanced U(VI) sorption significantly at pH?<?5.0, while decreased U(VI) sorption obviously at pH?>?9.0. The characteristic fluorescence changes of HA indicated that a strong chemical reaction occurred between the functional groups in HA and UO22+. The sorption was a spontaneous and endothermic process with increased entropy, and the increase in temperature would benefit the sorption.  相似文献   

12.
《Analytical letters》2012,45(8):1635-1644
ABSTRACT

The stepwise formation constants of Ce3+, Th4+ and UO2 2+ complexes with four azo compounds based on I-phenyl-2, 3-dimethylpyrazoline-5-one nucleus namely; 4-phenylazo- (2-hydroxy, 5-x) 1-pheny1-2, 3-dimethy1-pyrazoline-5-one, where x= H (1), OH (II), COOH (III) and NH2 (IV) have been determined potentiometrically at different temperatures and ionic strengths in 30% (v/v) ethanol-water solutions, then the thermodynamic parameters are calculated.

Negatives values of both ∠H and ∠G are obtained indicating the exothermic and spontaneous nature of complexation reactions, whereas positive values of ∠S show that entropy consideration favour complex formation. The study at different ionic strengths shows that an increase in the latter causes a decrese in the pK values. The azo compounds are also tested as new reagents for the spectrophotometric determination of Ce3+, Th4+ and UO2 2+ ions in synthetic and natural solutions by extensive investigation of the optimum conditions favoring the formation of colored complexes.  相似文献   

13.
Although a high heterogeneity of composition is awaited for humic substances, their complexation properties do not seem to greatly depend on their origins. The information on the difference in the structure of these complexes is scarce. To participate in the filling of this lack, a study of the spectral and temporal evolution of the Eu(III) luminescence implied in humic substance (HS) complexes is presented. Seven different extracts, namely Suwannee River fulvic acid (SRFA) and humic acid (SRHA), and Leonardite HA (LHA) from the International Humic Substances Society (USA), humic acid from Gorleben (GohyHA), and from the Kleiner Kranichsee bog (KFA, KHA) from Germany, and purified commercial Aldrich HA (PAHA), were made to contact with Eu(III). Eu(III)-HS time-resolved luminescence properties were compared with aqueous Eu3+ at pH 5. Using an excitation wavelength of 394 nm, the typical bi-exponential luminescence decay for Eu(III)-HS complexes is common to all the samples. The components τ1 and τ2 are in the same order of magnitude for all the samples, i.e., 40 ≤ τ1 (μs) ≤ 60, and 145 ≤ τ2 (μs) ≤ 190, but significantly different. It is shown that different spectra are obtained from the different groups of samples. Terrestrial extract on the one hand, i.e. LHA/GohyHA, plus PAHA, and purely aquatic extracts on the other hand, i.e., SRFA/SRHA/KFA/KHA, induce inner coherent luminescent properties of Eu(III) within each group. The 5D0 → 7F2 transition exhibits the most striking differences. A slight blue shift is observed compared to aqueous Eu3+ (λmax = 615.4 nm), and the humic samples share almost the same λmax ≈ 614.5 nm. The main differences between the samples reside in a shoulder around λ ≈ 612.5 nm, modelled by a mixed Gaussian–Lorentzian band around λ ≈ 612 nm. SRFA shows the most intense shoulder with an intensity ratio of I612.5/I614.7 = 1.1, KFA/KHA/SRHA share almost the same ratio I612.5/I614.7 = 1.2–1.3, whilst the LHA/GohyHA/PAHA group has a I612.5/I614.5 = 1.5–1.6. This shows that for the two groups of complexes, despite comparable complexing properties, slightly different symmetries are awaited.  相似文献   

14.
The effect of Aldrich humic acid (HA) on the mobility of137Cs,85Sr,152Eu and239Pu radionuclides was studied in Ca-montmorillonite suspensions. Verified 2-sites-2-species (2s2s) models correspond to an intensive interaction of all elements with humificated surface, what is in a remarkable contrast with the weak complexation of cesium and even strontium in solutions — the neutral ligand interaction constants β (l/mol) are log β<−9.9 and 7.56±0.21 for Cs and Sr, respectively. The result for europium complexation in solution, log β=12.49±0.18 is in a good agreement with literature data. For plutonium(IV) not only a high proton competitive constant in solution was obtained, log β β=(−0.67±0.32)+3pH, but also a strong chemisorption, which at high concentrations of humic acid (above 0.05 g/l) indicates the formation of bridge humate complexes of plutonium on the humificated surface. Logarithms of heterogeneous interaction constants ( 24 l/g) of the elements with surface humic acid are 4.47±0.23, 4.39±0.08, and 6.40±0.33 for Cs, Sr, and Eu(III), respectively, and the logarithm of the proton competitive constant ( 24, l/g) for Pu(IV) −3.80±0.72. Distribution coefficients of humic acid and metal humates between 0.01 g HA/l solution and montmorillonite were derived as logK d(AH)=−1.04±0.11, logK d(EuA)=1.56±0.11 and logK d(PuA)=2.25±0.04, while the values for Cs and Sr were obtained with very high uncertainty. Speciation of the elements on montmorillonite surface is illustrated as a function of equilibrium concentration of humic acid in solution and of pH.  相似文献   

15.
《Comptes Rendus Chimie》2002,5(5):395-404
A series of substituted 2,3-dihydroxyterephthalamides has been prepared and investigated by means of potentiometry, spectrophotometry and 1H NMR spectroscopy at 25 °C. Proton association constants for the ligand and formation constants for the ferric complexes are as follows: 2,3-dihydroxy-N,N’-diethylterephthalamide, log β011 = 10.83, log β012 = 17.09, log β110 = 17.27, log β120 = 31.59, log β130 = 42.67; 2,3-dihydroxy-N,N’-bis(2-hydroxyethyl)terephthalamide, log β011 = 10.61, log β012 = 16.66, log β110 = 17.04, log β120 = 31.0, log β130 = 42.1; 2,3-dihydroxy-N,N’-bis(ethanesulfonate)terephthalamide disodium salt, log β011 = 11.01, log β012 = 17.48, log β110 = 18.24, log β120 = 31.72, log β130 = 40.3; 2,3-dihydroxy-N,N’-bis(N,N-dimethylaminoethyl)terephthalamide dihydrobromide salt, log β011 = 10.86, log β012 = 20.10, log β013 = 28.53, log β014 = 33.92, log β110 = 17.4, log β120 = 32.5, log β130 = 45.2. The equilibrium free metal ion concentrations (–log 〚Fe3+〛 = pM) of these ligands are compared and discussed.  相似文献   

16.
Complexation of the uranyl ion (UO22+) and of the peroxouranyl species (UO4) by some polyaminocarboxylate ligands has been investigated in solution (3M NaClO4) at 25°C. The logarithms of the cumulative formation constants of the UO22+ chelates formed are: UO2edta2? (15.65), UO2Hedta? (18.59), (UO2)2edta (20.24); UO2edda (16.02); UO2Hnta (12.19); UO2ida (9.63), UO2H2(ida)2 (23.80). The equilibrium UO22+ + H2O2 ? UO4 + 2H+ has a stability log K = ?3.99. The peroxocomplexes formed are UO4Hedda? (14.81, expressed from UO22+ and H2O2) and UO4Hnta2? (8.50). Solution structures of the chelates are proposed.  相似文献   

17.
The study of radionuclides speciation requires accurate evaluation of stability constants, which can be achieved by CE‐ICPMS. We have previously described a method for 1:1 metal complexes stability constants determination. In this paper, we present its extension to the case of successive complexations and its application to uranyl‐oxalate and lanthanum‐oxalate systems. Several significant steps are discussed: analytical conditions choice, mathematical treatment by non‐linear regression, ligand concentration and ionic strength corrections. The following values were obtained: at infinite dilution, log(β1°(UO2Oxa))=6.93±0.05, log(β2°(UO2(Oxa)22?))=11.92±0.43 and log(β3°(UO2(Oxa)34?))=15.11±0.12; log(β1°(LaOxa+))=5.90±0.07, log(β2°(La(Oxa)2?))=9.18±0.19 and log(β3°(La(Oxa)33?))=9.81±0.33. These values are in good agreement with the literature data, even though we suggest the existence of a new lanthanum‐oxalate complex: La(Oxa)33?. This study confirms the suitability of CE‐ICPMS for complexation studies.  相似文献   

18.
The complexation of uranyl ion (UO22+) in aqueous solution with polymers containing carboxylic acid groups was studied potentiometrically. Overall formation constants of the uranyl complexes with poly(methacrylic acid) and crosslinked poly(acrylic acid) were much larger than those with the corresponding low molecular carboxylic acids. Decrease in the viscosity of the polymer solution on adding uranyl ion indicated that poly(acrylic acid) forms intra-polymer chelates with uranyl ion. The crosslinked poly(acrylic acid) adsorbed uranyl ions at higher efficiency than transition metal ions.  相似文献   

19.
The formation constants of dioxouranium(VI)-2,2′-oxydiacetic acid (diglycolic acid, ODA) and 3,6,9-trioxaundecanedioic acid (diethylenetrioxydiacetic acid, TODA) complexes were determined in NaCl (0.1≤I≤1.0 mol⋅L−1) and KNO3 (I=0.1 mol⋅L−1) aqueous solutions at T=298.15 K by ISE-[H+] glass electrode potentiometry and visible spectrophotometry. Quite different speciation models were obtained for the systems investigated, namely: ML0, MLOH, ML22−, M2L2(OH), and M2L2(OH)22−, for the dioxouranium(VI)–ODA system, and ML0, MLH+, and MLOH for the dioxouranium(VI)–TODA system (M=UO22+ and L = ODA or TODA), respectively. The dependence on ionic strength of the protonation constants of ODA and TODA and of both metal-ligand complexes was investigated using the SIT (Specific Ion Interaction Theory) approach. Formation constants at infinite dilution are [for the generic equilibrium pUO22++q(L2−)+rH+ (UO22+) p (L) q H r (2p−2q+r);β pqr ]: log 10 β 110=6.146, log 10 β 11−1=0.196, log 10 β 120=8.360, log 10 β 22−1=8.966, log 10 β 22−2=3.529, for the dioxouranium(VI)–ODA system and log β 110=3.636, log 10 β 111=6.650, log 10 β 11−1=−1.242 for dioxouranium(VI)–TODA system. The influence of etheric oxygen(s) on the interaction towards the metal ion was discussed, and this effect was quantified by means of a sigmoid Boltzman type equation that allows definition of a quantitative parameter (pL 50) that expresses the sequestering capacity of ODA and TODA towards UO22+; a comparison with other dicarboxylates was made. A visible absorption spectrum for each complex reaching a significant percentage of formation in solution (KNO3 medium) has been calculated to better characterize the compounds found by pH-metric refinement.  相似文献   

20.
The effect of radioactive UO22+ on the oxygen‐transporting capability of hemoglobin‐based oxygen carriers has been investigated in vitro. The hemoglobin (Hb) microspheres fabricated by the porous template covalent layer‐by‐layer (LbL) assembly were utilized as artificial oxygen carriers and blood substitutes. Magnetic nanoparticles of iron oxide (Fe3O4) were loaded in porous CaCO3 particles for magnetically assisted chemical separation (MACS). Through the adsorption spectrum of magnetic Hb microspheres after adsorbing UO22+, it was found that UO22+ was highly loaded in the magnetic Hb microspheres, and it shows that the presence of UO22+ in vivo destroys the structure and oxygen‐transporting capability of Hb microspheres. In view of the high adsorption capacity of UO22+, the as‐assembled magnetic Hb microspheres can be considered as a novel, highly effective adsorbent for removing metal toxins from radiation‐contaminated bodies, or from nuclear‐power reactor effluent before discharge into the environment.  相似文献   

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